2009 DOE Hydrogen Program Review Electron-Charged Hydrogen

Storage Materials

Chinbay Q. FanGas Technology Institute

May 20, 2009 Project ID #STP_02_fan

This presentation does not contain any proprietary, confidential, or otherwise restricted information

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Overview

Project start:  July 1, 2005 Project end: Sept 30, 2010 Percent complete: 55%

Cost: use inexpensive graphiteWeight and volume: use high density graphite, maximizing capacityEfficiency: add electron charge to increase storage rateDurability: use electron charge to control cyclesRefueling Time: use electron charge to increase fueling rateCodes and StandardsSystem Life‐Cycle Assessments

Total project fundingDOE share: $1,562KContractor share: $390K

Funding received in FY08: $275,785Funding for FY09: $303,010

Timeline

Budget

Barriers

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Objectives

Overall Development of a hydrogen storage material and device for hydrogen quick charge and discharge, high wt% and vol% storage capacities, good durability over many cycles, and safe handling and transport.

2008 • Combine internal electron-charge (doping) and external charge to increase hydrogen storage capacities

• Investigate performance optimization and prototype container systems

2009 • Reselect the best hydrogen storage materials for charge modifications

• Carbon-based materials, such as AX-21 and other high surface carbon using polymer as precursor; metal-modified carbon; and borane-ammonia

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Month/Year Milestone or Go/No-Go DecisionSept., 2008 Task 1. Test and evaluate cycles for hydrogen storage

Modify the electron charge distribution structure (Framework structure) to obtain a 50% hydrogen storage rate increase.Fueling kinetics study: does the electron charge make desorption fast?Theoretical calculation: how much charge is needed to get 6 wt%?

Task 2. Observe and detect charge distribution under electrostatic charge.

Task 3. Optimize charge control agent (CCA) and charge transfer agent (CTA) to help polarizing storage materials.

Milestone or Go/No-Go Decision

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Milestone or Go/No-Go Decision

Month/Year Milestone or Go/No-Go Decision

July 30, 2009 Task 4. Characterize the electron device and the material properties of the carbon based material with CCA/CTA (pore size, density, surface area, etc)

Task 5. Prepare samples for independent evaluation.Install framework structure to improve charge distribution

Task 6. Scale-up to an 11 liter tank for fueling demonstration to show 50% hydrogen storage increase.

Multi-kilogram samples/prototype system containers: 11 liter tank for fueling demonstration to show a 50% hydrogen storage increase.

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Approach

Hydrogen storage is based on hydrogen adsorption, which is involved in electron shift (physi-sorption) and electron transfer (chemi-sorption).

Use external electron charge to increase hydrogen adsorption and alter hydrogen desorption kinetics.

Use internal electron-rich or -poor material to change carbon-based material surface electron density, which affects hydrogen storage.

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Plan and Approach

• Select and synthesize carbon-based materials

• Test and evaluate cycles for hydrogen storage

• Test external electron charge effect on hydrogen storage

• Dynamic TGA and Sievert Tests

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Approach

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Metal modified AX-21 shows electrostatic effect at low pressure at room temperature

Technical Accomplishment and Progress

Metal modified carbon shows positive effect under positive polarization

21% increase

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Technical Accomplishment and ProgressElectro-static polarization also affects desorption: positive charge makes desorption slower (ca. 10% at 1MPa), negative charge faster

Metal modified carbon has positive effect under positive polarization at room temperature. Des no V is overlap to ads no V. 5 min per data

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Technical Accomplishment and ProgressElectro-static polarization has less effect on the metal modified AX-21 at Storage at 77K

Metal modification decreases low temperature physical adsorption because the kinetics is slow

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Technical Accomplishment and Progress

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Technical Accomplishment and Progress

Cyclic voltammograms show NO internal short was observed in the system and verify that the adsorption increase/decrease was NON-Faradaic.

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Technical Accomplishment and Progress

1.00g borane-nitride with 0.05g catalyst at 80°C

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Non-faradaic Electrochemical Modification of Catalysis (NEMCA) Increases the Hydrogen Release Rate

1.00g boron-nitride 0.05g catalyst at 80°C even at 900 psi

Ref. slide 14, at 900 psi, the decomposition of borane nitride for 1.5 wt% takes 2.5 hours without electrical charge, only 40 minutes with negative charge. The decomposition rate under electrical charge at different pressures will be generated.

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Electron Charges Increase Hydrogen Storage

1.00g boron-nitride 0.05g catalyst at 80°C. The threshold point occurs when pressure increases to 6MPa with negative charge

75% increase

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Technical Accomplishment and Progress

Hydrogen Storage Material Screening without Electrical Charge

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Technical Accomplishment and Progress

Hydrogen Storage Material Screening without Electrical Charge

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Summary of SUNY samples at 6300kPaSample name R.T. (wt%) 77k (wt%)

APPANNI(2) 0.52 6.49

APKI6S2 0.40 6.98

MK775 0.44 5.82

PK-NaH-1-1 0.38 4.41

APTPN1 0.49 6.42

Technical Accomplishment and Progress

Hydrogen Storage Material Screening without Electrical Charge

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Proposed Future Work

Continue boron nitride (hydrogen storage more than 6 wt%) research and external charge bias to increase the hydrogen storage rate. Characterize the external charge effect on material physical and chemical properties (pore size, density, surface area, etc).

Prepare samples for independent evaluation.Install framework structure to improve charge

distribution.Scale-up to an 11 liter tank for fueling demonstration to

show 50% hydrogen storage increase.

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Conclusions

External electron charge does affect the hydrogen storage, however different substrates shows different effects

For metal modified AX-21, at 2MPa, the hydrogen storage rate increased approximately 20% using positive charge

Negative charge helps boron nitride dehydrogenation kinetics (4 times faster at 900psi) and increases the reversible hydrogenation

External charge effect on pure carbon material is limited.

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Cooperation

State University of New York at Syracuse: Prof. Cabasso group

Japanese CCA Manufacturer

ATMI

University of Houston

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Acknowledgements

Financial Support by DOE: DE-FG36-05GO15010.

DOE Supervisors: Jesse J. Adams, Monterey Gardiner, Carole J. Read, Sunita Satyapal

State University of New York at Syracuse: Prof. Cabasso group

Japanese CCA Manufacturer

ATMI